US20190211286A1 - Sulfoxide/Glycol Ether Based Solvents for Use in the Electronics Industry - Google Patents
Sulfoxide/Glycol Ether Based Solvents for Use in the Electronics Industry Download PDFInfo
- Publication number
- US20190211286A1 US20190211286A1 US15/544,310 US201715544310A US2019211286A1 US 20190211286 A1 US20190211286 A1 US 20190211286A1 US 201715544310 A US201715544310 A US 201715544310A US 2019211286 A1 US2019211286 A1 US 2019211286A1
- Authority
- US
- United States
- Prior art keywords
- component
- dimethyl
- solvent
- propionamide
- sulfoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003462 sulfoxides Chemical class 0.000 title claims abstract description 78
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000004210 ether based solvent Substances 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 108
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims abstract description 47
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 40
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 29
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims abstract description 27
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 17
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 claims abstract description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 10
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims abstract description 8
- YKOQQFDCCBKROY-UHFFFAOYSA-N n,n-diethylpropanamide Chemical compound CCN(CC)C(=O)CC YKOQQFDCCBKROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 25
- 238000007710 freezing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- -1 e.g. Chemical compound 0.000 abstract description 19
- 239000004065 semiconductor Substances 0.000 abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 153
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 55
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 46
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000005977 Ethylene Substances 0.000 description 28
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- XQZDWKBCGAJXLC-UHFFFAOYSA-N n-butylpropanamide Chemical compound CCCCNC(=O)CC XQZDWKBCGAJXLC-UHFFFAOYSA-N 0.000 description 13
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 229940080818 propionamide Drugs 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- PXQDWZWVJXQXDH-UHFFFAOYSA-N C(CC)(=O)N.C(CCC)OCCCC Chemical compound C(CC)(=O)N.C(CCC)OCCCC PXQDWZWVJXQXDH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- KCHJYFPVDJUBAP-UHFFFAOYSA-N 1-butoxybutane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCOCCCC KCHJYFPVDJUBAP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 2
- 231100000615 substance of very high concern Toxicity 0.000 description 2
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YTGKHEDTLHRZGX-RWSKJCERSA-N n-(cyclopentylmethyl)-n-[(2s)-3-[(3s,5r)-3,5-dibenzyl-2-oxopyrrolidin-1-yl]-2-hydroxypropyl]-4-methoxybenzenesulfonamide Chemical compound C1=CC(OC)=CC=C1S(=O)(=O)N(CC1CCCC1)C[C@@H](O)CN1C(=O)[C@@H](CC=2C=CC=CC=2)C[C@@H]1CC1=CC=CC=C1 YTGKHEDTLHRZGX-RWSKJCERSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3445—Organic compounds containing sulfur containing sulfino groups, e.g. dimethyl sulfoxide
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/362—Phosphates or phosphites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0005—Special cleaning or washing methods
- C11D11/0011—Special cleaning or washing methods characterised by the objects to be cleaned
- C11D11/0023—"Hard" surfaces
- C11D11/0047—Electronic devices, e.g. PCBs or semiconductors
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- C11D2111/22—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
Definitions
- This invention relates to ecology-friendly solvents (“eco-solvents”) useful in the manufacture of various electronic components, e.g., display units and semiconductors.
- eco-solvents useful in the manufacture of various electronic components, e.g., display units and semiconductors.
- NMP N-methyl-2-pyrrolidone
- DMAc dimethyl acetamide
- DMF dimethyl formamide
- NMP N-methyl-2-pyrrolidone
- GLS European Globally Harmonized System of Classification and Labeling of Chemicals
- REACH Annex XVII REACH Annex XVII
- NMP is used in the electronics industry for cleaning and stripping of various parts (e.g., components for display units, semiconductor substrates, etc.) and equipment, and considerable amounts of it are consumed annually. Developing an eco-solvent to achieve similar performance with a better environmental profile than NMP is an urgent request from electronic processing customers.
- This invention details solvent combinations that, in some embodiments, provide the same or better cleaning ability, and stripping ability for photoresist removal, than NMP.
- the invention is a process for cleaning or stripping the surface of a substrate, the process comprising the step of contacting the substrate with a solvent consisting essentially of:
- the numerical ranges disclosed herein include all values from, and including, the lower and upper value.
- explicit values e.g., 1 to 7
- any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
- compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
- the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability.
- the term “consisting of” excludes any component, step, or procedure not specifically delineated or listed.
- solvent and like terms mean a substance that is capable of dissolving another substance (i.e., a solute) to form an essentially uniformly dispersed mixture (i.e., solution) at the molecular or ionic size level.
- Electronic part and like terms mean an in-process or finished product, or component of a product, of a manufacturing process for electronic goods, such as a semiconductor or display unit.
- Electronic part as used in the context of this invention, includes the equipment used to manufacture the product.
- In-process product and like terms mean an unfinished or intermediate product. In-process products include starting materials, e.g., materials as received from vendors, or materials before subjected to the start of the manufacturing process.
- Photoresist and like terms mean a photosensitive resin that loses its resistance to chemical etching when exposed to radiation and is used especially in the transference of a circuit pattern to a semiconductor chip during the production of an integrated circuit.
- “Cleaning” and like terms mean, in the context of this invention, the removal of particulate contamination and metal ions from the surface of a substrate, usually from the surface of an in-process electronic part to ready the part for subsequent processing.
- “Stripping” and like terms mean, in the context of this invention, the removal of a layer, e.g., coating or film, from the surface of a substrate, such as the removal of a photoresist from the surface of a semiconductor substrate.
- Freezing point and like terms mean the temperature at which a liquid changes into a solid.
- the freezing point of the solvents of this invention can be determined by using test equipment that includes a glass container, cooling bath or cooling trap or refrigerator with temperature control system, and thermometer or thermal sensor.
- a twenty gram (20 g) sample of liquid solvent is placed in a glass container, e.g., a glass cylinder.
- the temperature of the cooling bath or cooling trap or refrigerator is set at 0° C.
- a thermometer or thermal sensor is used to determine the temperature of cold liquid or cold airflow inside of cooling bath or cooling trap or refrigerator.
- the glass container with prepared solvent sample is stored in the cooling bath or cooling trap for at least 12 hours.
- the freezing point of the solvent sample is determined by observing its physical state, i.e., liquid or solid. If the solvent sample still shows fluidity, the current setting temperature of the cooling bath or cooling trap or refrigerator is reduced until its temperature determined by thermometer or thermal sensor is 1° C. less than its previous temperature. The procedure is repeated until the solvent sample is solid.
- Poly(amic acid) is an intermediate polymer in the synthesis of polyimide. It is soluble in polar solvents due to strong hydrogen bonding.
- Polyimide is a polymer of imide monomers. It is normally produced by the reaction of a dianhydride and a diamine.
- PI polyimide
- KAPTONTM It is produced from the condensation of pyromellitic dianhydride and 4,4′-oxydiphenylamine.
- the solvents of this invention consist essentially of a first component, a second component, and a third component.
- the first component consists of, or is, a sulfoxide.
- the second component consists of, or is, a glycol ether.
- the third component consists of, or consists essentially of, at least one of N-formyl morpholine (CAS Number 4394-85-8), N,N-dimethyl propionamide (CAS Number 758-96-3), 3-methoxy-N,N-dimethyl propanamide (CAS Number 53185-52-7), triethyl phosphate (CAS Number 78-40-0), N,N-dimethyl acetamide (CAS Number 127-19-5); N,N-diethyl acetamide (CAS Number 685-91-6), N,N-diethyl propionamide (CAS Number 1114-51-8), N-methyl acetamide (CAS Number 79-16-3), N-methyl propionamide (CAS Number 1187-58-2), N-ethy
- the first component of the solvent of this invention consists of, or is, a sulfoxide, i.e., a compound containing a sulfinyl functional group attached to two carbon atoms. It is a polar functional group.
- Sulfoxides are the oxidized derivatives of sulfides. Representative sulfoxides include, but are not limited to, diethyl sulfoxide, butyl sulfoxide, tetramethylene sulfoxide and dimethyl sulfoxide (DMSO).
- the first component can consist of one or more sulfoxides. In one embodiment the first component consists of one sulfoxide. In one embodiment the first component consists of two or more sulfoxides. In one embodiment the first component consists of, or is, DMSO (CAS Number 67-68-5).
- the second component of the solvent of this invention consists of, or is, a glycol ether, i.e., a compound based on an alkyl ether of ethylene glycol or propylene glycol.
- glycol ethers typically have a higher boiling point, together with the favorable solvent properties of lower-molecular weight ethers and alcohols.
- Representative glycol ethers include, but are not limited to, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
- the second component can consist of one or more glycol ethers.
- the second component consists of one glycol ether. In one embodiment the second component consists of two or more glycol ethers. In one embodiment the second component is an ethylene glycol alkyl ether. In one embodiment the second component is a propylene glycol alkyl ether. In one embodiment the alkyl component of the ethylene or propylene glycol ether is an alkyl group of 2 to 12, or 3 to 10, or 3 to 8, carbon atoms. In one embodiment the second component consists of, or is, ethylene glycol monobutyl ether (CAS Number 111-76-2).
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and N-formyl morpholine as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and N,N-dimethyl propionamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and triethyl phosphate as the third component.
- the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and N-formyl morpholine as the third component.
- the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and N,N-dimethyl propionamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and triethyl phosphate as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and N-formyl morpholine as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and N,N-dimethyl propionamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and triethyl phosphate as the third component.
- the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and N-formyl morpholine as the third component.
- the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and N,N-dimethyl propionamide as the third component.
- the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a tertiary blend consisting of, or consisting essentially, of DMSO as the first component, ethylene glycol monobutyl ether as the second component, and triethyl phosphate as the third component.
- the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and N,N-dimethyl propionamide as the third component.
- the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and triethyl phosphate as the third component.
- the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide and triethyl phosphate as the third component.
- the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide and 3-methoxy-N,N-dimethyl propanamide as the third component.
- the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide and triethyl phosphate as the third component.
- the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- the solvent is a senary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 50 to 90 wt % of the first component, from 9 to 40 wt % of the second component, and from 1 to 30 wt % of the third component.
- the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 50 to 90 wt % of DMSO, from 9 to 40 wt % of ethylene glycol monobutyl ether, and from 1 to 30 wt % of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of the first component, from 1 to 30 wt % of the second component, and from 70 to 90 wt % of the third component.
- the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of DMSO, from 10 to 30 wt % of ethylene glycol monobutyl ether, and from 70 to 90 wt % of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide, triethyl phosphate, N,N-dimethyl acetamide; N,N-diethyl acetamide, N,N-diethyl propionamide, N-methyl acetamide, N-methyl propionamide, N-ethyl acetamide, and N-ethyl propionamide as the third component.
- the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of DMSO, from 10 to 30 wt % of ethylene glycol monobutyl ether, and from 70 to 90 wt % of N,N-dimethyl propionamide, as the third component.
- the solvent has a freezing point of less than ( ⁇ ) ⁇ 25° C., or ⁇ 20° C., or ⁇ 15° C., or ⁇ 10° C. In one embodiment the solvent has a freezing point from ⁇ 25° C. or less to ⁇ 10° C. or more.
- the third component consists of more than one substance, e.g., the third component consists essentially of N-formyl morpholine and N,N-dimethyl propionamide and/or 3-methoxy-N,N-dimethyl propanamide and/or triethyl phosphate, etc.
- the amount of each compound in the third component can vary widely and to convenience.
- the amount of each individual substance in the third component can vary from 0 to 100 wt %, or from 1 to 99 wt %, or from 10 to 90 wt %, or from 20 to 80 wt % or from 30 to 70 wt %, or from 40 to 60 wt %, or 50 wt %, based on the weight of the component.
- Optional materials that are not essential to the operability of, but can be included in, the solvents of this invention include, but are not limited to, antioxidants, colorants, water scavengers, stabilizers, and the like. These materials do not have any material impact on the efficacy of the solvent for cleaning or stripping electronic parts. These optional materials are used in known amounts, e.g., 0.10 to 5, or 4, or 3, or 2, or 1, weight percent based on the weight of the solvent, and they are used in known ways.
- the solvents of this invention are made using known equipment and known techniques.
- the individual components of the solvent are commercially available, liquid at ambient conditions (23° C. and atmospheric pressure), and can simply be mixed with one another using conventional mixing equipment and standard blending protocols.
- the components can be added to one another in any order including simultaneously.
- the solvents of this invention are eco-solvents, i.e., they do not have, or have at a reduced level, the toxicology issues associated with NMP. These solvents are useful for cleaning and/or stripping the surfaces of substrates of contaminants and other unwanted substances, particularly polar contaminants and polar unwanted substances.
- the solvents of this invention are intended as a replacement for NMP and other polar solvents used in the electronics industry. As such, they are used in the same manner as NMP and the other polar solvents in such operations as cleaning and stripping of electronic parts and equipment, and the removal of photoresists from various substrates, e.g., semiconductor substrates, and the removal of polyamic acid polymer residue from polyimide coating equipment, e.g., alignment layer and flexible display substrate coating machine.
- these methods or processes include the step of contacting the object or substrate to be cleaned or stripped, or from which a photoresist or a polyamic acid/polyimide residue is to be removed, with the solvent under any of various conditions, e.g., ambient conditions, or at an elevated or reduced temperature, with or without flow or agitation, e.g., printing, spinning, immersing, flushing, vibrating, showering, spraying, etc., for a sufficient period of time to dissolve whatever material, e.g., a contaminant such as poly(amic acid)/polyimide residue, dianhydride, diamine, etc.; a photoresist, and the like, that is to be removed.
- a contaminant such as poly(amic acid)/polyimide residue, dianhydride, diamine, etc.
- This contacting step is then typically followed by rinse (one or more, typically with an aqueous liquid such as deionized water) and drying steps.
- Solvents with a freezing temperature of less than ⁇ 25° C. can be particularly favored for use in the processes of cleaning and/or stripping electronic parts and equipment.
- Poly(amic acid), precursor of polyimide poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid (from Sigma-Aldrich, 15 ⁇ 16 wt % dissolved in NMP).
- Photoresist SFP-1400 (from Merck).
- the solvents are designed according to Hansen Solubility Parameter of NMP, DMF, 3-methoxy-N,N-dimethyl propanamide, etc. These commercialized solvents have strong dissolution ability for most electronic materials.
- the solvents are described in Table 1.
- Poly(amic acid) dissolution A solution of poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid precursor in NMP is contacted with deionized (DI) water or other NMP-insoluble liquid to extract the precursor from the NMP.
- DI deionized
- the poly(amic acid) precursor is then baked at 54° C. for 4 hours to evaporate any residual solvent/liquid before it is dissolved by contact with the test solvent. Results are recorded after 12 hours at 54° C.
- Photoresist stripping Place 2 milliliters (ml) SFP-1400 photoresist solution onto the surface of glass substrate with a size of 100 millimeters (mm) ⁇ 100 mm ⁇ 1 mm.
- the substrate is spun with a rotation speed of 500 revolutions per minute (rpm) for 10 seconds (s) to spread out the photoresist solution.
- the rotation speed is then accelerated to 1000 rpm for 30 s to coat the photoresist homogenously and spin out redundant solvent.
- the coated substrate is heated to evaporate solvent at 130° C. for 10 minutes (min).
- the stripping step prepares 30 grams (g) example in the container.
- the baked substrate is placed into the container with shaking, and finally the time is measured for completely removing photoresist from the substrate.
- Poly(amic acid) dissolution The poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid solubility results of each product are reported in Table 2. The content of polymer in each example and comparative sample is 20% by weight. The performance is judged through the fluidity of the solution.
- the two examples N-formyl morpholine/N,N-dimethyl propionamide, and dimethyl sulfoxide/N,N-dimethyl propionamide exhibit good fluidity with low viscosity.
- N-formyl morpholine/3-methoxy-N,N-dimethyl propanamide shows a certain fluidity and suitable viscosity.
- Photoresist stripping The photoresist stripping results of each combination are listed in Table 3. The performance is evaluated by stripping time.
- the example dimethyl sulfoxide/ethylene glycol monobutyl ether/N,N-dimethyl propionamide can completely strip the coated photoresist from the glass substrate within 15 seconds.
- the other invented dimethyl sulfoxide/ethylene glycol monobutyl ether based examples require 15 to 20 seconds to strip the photoresist.
- Water based monoethanolamine/diethylene glycol butyl ether and monoethanolamine/N-methyl-2-pyrrolidone comparative samples Dongji (KR1403516B1) need almost a half-minute for stripping.
- monoethanolamine/diethylene glycol butyl ether without water content shows relatively slow stripping speed. Therefore, the examples possess better stripping performance on SFP-1400 photoresist.
- the solvents are designed to have a freezing point lower than ⁇ 25° C., and faster photoresist stripping and polyamic acid dissolution than NMP.
- the detailed ratio for each inventive and comparative example is reported in the Table 4.
- the poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid solubility results of each product are reported in Table 5.
- the amount of polymer in each example and comparative sample is 30% by weight.
- the performance is judged through the viscosity of the solution. All dimethyl sulfoxide/ethylene glycol monobutyl ether based solvents can completely dissolve polyamic acid and exhibit good viscosity, which indicates the invented combinations have equivalent performance with N-methyl-2-pyrrolidone.
- 3-methoxy-N,N-dimethyl propanamide the related solubility is comparatively lower.
- the solution is hard to flow. Therefore, the solvency for polyamic acid of the inventive examples is good relative to certain commercial products.
- the photoresist stripping results of each combination are reported in Table 6.
- the performance is evaluated by stripping time.
- Dimethyl sulfoxide/ethylene glycol monobutyl ester/N,N-dimethyl propionamide can completely strip the coated photoresist from the glass substrate within 15 seconds.
- the dimethyl sulfoxide/ethylene glycol monobutyl ester based examples require 15 to 20 seconds to strip the photoresist.
- Water-based monoethanolamine/diethylene glycol butyl ether and monoethanolamine/N-methyl-2-pyrrolidone comparative samples required close to a half minute for stripping.
- monoethanolamine/diethylene glycol butyl ether without water content shows relatively slow stripping speed. Therefore, the examples possess better stripping performance on SFP-1400 photoresist.
Abstract
-
- (A) a first component consisting of a sulfoxide, e.g., DMSO;
- (B) a second component consisting of a glycol ether, e.g., ethylene glycol monobutyl ether; and
- (C) a third component consisting of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide, triethyl phosphate, N,N-dimethyl acetamide; N,N-diethyl acetamide, N,N-diethyl propionamide, N-methyl acetamide, N-methyl propionamide, N-ethyl acetamide, and N-ethyl propionamide.
Description
- This invention relates to ecology-friendly solvents (“eco-solvents”) useful in the manufacture of various electronic components, e.g., display units and semiconductors.
- Some polar solvents, e.g., N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl formamide (DMF), etc., have reproductive toxicity, which drive the ever increasing global safety and regulatory concerns related to these materials. For example, NMP is listed in the Substance of Very High Concerns (SVHC) registry of the European Globally Harmonized System of Classification and Labeling of Chemicals (GHS) and REACH Annex XVII which lists the restrictions on the manufacture, placing on the market and use of certain dangerous substances, mixtures and articles.
- NMP is used in the electronics industry for cleaning and stripping of various parts (e.g., components for display units, semiconductor substrates, etc.) and equipment, and considerable amounts of it are consumed annually. Developing an eco-solvent to achieve similar performance with a better environmental profile than NMP is an urgent request from electronic processing customers. This invention details solvent combinations that, in some embodiments, provide the same or better cleaning ability, and stripping ability for photoresist removal, than NMP.
- In one embodiment the invention is a solvent consisting essentially of:
- and
-
- (A) a first component consisting of a sulfoxide;
- (B) a second component consisting of a glycol ether; and
- (C) a third component consisting of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide, triethyl phosphate, N,N-dimethyl acetamide; N,N-diethyl acetamide, N,N-diethyl propionamide, N-methyl acetamide, N-methyl propionamide, N-ethyl acetamide, and N-ethyl propionamide.
- In one embodiment the invention is a process for cleaning or stripping the surface of a substrate, the process comprising the step of contacting the substrate with a solvent consisting essentially of:
-
- (A) a first component consisting of a sulfoxide;
- (B) a second component consisting of a glycol ether; and
- (C) a third component consisting of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide, triethyl phosphate, N,N-dimethyl acetamide; N,N-diethyl acetamide, N,N-diethyl propionamide, N-methyl acetamide, N-methyl propionamide, N-ethyl acetamide, and N-ethyl propionamide.
- For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
- The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., 1 to 7), any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
- The terms “comprising,” “including,” “having,” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step, or procedure not specifically delineated or listed. The term “or,” unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.
- Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure.
- “Solvent” and like terms mean a substance that is capable of dissolving another substance (i.e., a solute) to form an essentially uniformly dispersed mixture (i.e., solution) at the molecular or ionic size level.
- “Electronic part” and like terms mean an in-process or finished product, or component of a product, of a manufacturing process for electronic goods, such as a semiconductor or display unit. Electronic part, as used in the context of this invention, includes the equipment used to manufacture the product.
- “In-process product” and like terms mean an unfinished or intermediate product. In-process products include starting materials, e.g., materials as received from vendors, or materials before subjected to the start of the manufacturing process.
- “Photoresist” and like terms mean a photosensitive resin that loses its resistance to chemical etching when exposed to radiation and is used especially in the transference of a circuit pattern to a semiconductor chip during the production of an integrated circuit.
- “Cleaning” and like terms mean, in the context of this invention, the removal of particulate contamination and metal ions from the surface of a substrate, usually from the surface of an in-process electronic part to ready the part for subsequent processing.
- “Stripping” and like terms mean, in the context of this invention, the removal of a layer, e.g., coating or film, from the surface of a substrate, such as the removal of a photoresist from the surface of a semiconductor substrate.
- “Freezing point” and like terms mean the temperature at which a liquid changes into a solid. The freezing point of the solvents of this invention can be determined by using test equipment that includes a glass container, cooling bath or cooling trap or refrigerator with temperature control system, and thermometer or thermal sensor. A twenty gram (20 g) sample of liquid solvent is placed in a glass container, e.g., a glass cylinder. The temperature of the cooling bath or cooling trap or refrigerator is set at 0° C. A thermometer or thermal sensor is used to determine the temperature of cold liquid or cold airflow inside of cooling bath or cooling trap or refrigerator. The glass container with prepared solvent sample is stored in the cooling bath or cooling trap for at least 12 hours. The freezing point of the solvent sample is determined by observing its physical state, i.e., liquid or solid. If the solvent sample still shows fluidity, the current setting temperature of the cooling bath or cooling trap or refrigerator is reduced until its temperature determined by thermometer or thermal sensor is 1° C. less than its previous temperature. The procedure is repeated until the solvent sample is solid.
- Poly(amic acid) is an intermediate polymer in the synthesis of polyimide. It is soluble in polar solvents due to strong hydrogen bonding.
- Polyimide (PI) is a polymer of imide monomers. It is normally produced by the reaction of a dianhydride and a diamine. One common PI used in the electronics industry is KAPTON™ It is produced from the condensation of pyromellitic dianhydride and 4,4′-oxydiphenylamine.
- The solvents of this invention consist essentially of a first component, a second component, and a third component. The first component consists of, or is, a sulfoxide. The second component consists of, or is, a glycol ether. The third component consists of, or consists essentially of, at least one of N-formyl morpholine (CAS Number 4394-85-8), N,N-dimethyl propionamide (CAS Number 758-96-3), 3-methoxy-N,N-dimethyl propanamide (CAS Number 53185-52-7), triethyl phosphate (CAS Number 78-40-0), N,N-dimethyl acetamide (CAS Number 127-19-5); N,N-diethyl acetamide (CAS Number 685-91-6), N,N-diethyl propionamide (CAS Number 1114-51-8), N-methyl acetamide (CAS Number 79-16-3), N-methyl propionamide (CAS Number 1187-58-2), N-ethyl acetamide (CAS Number 625-50-3), and N-ethyl propionamide (CAS Number 5129-72-6). The first, second and third components form a blend, and the blend may or may not be phase separated. In one embodiment the solvent has a freezing point of less than −25° C.
- Sulfoxides
- The first component of the solvent of this invention consists of, or is, a sulfoxide, i.e., a compound containing a sulfinyl functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are the oxidized derivatives of sulfides. Representative sulfoxides include, but are not limited to, diethyl sulfoxide, butyl sulfoxide, tetramethylene sulfoxide and dimethyl sulfoxide (DMSO). The first component can consist of one or more sulfoxides. In one embodiment the first component consists of one sulfoxide. In one embodiment the first component consists of two or more sulfoxides. In one embodiment the first component consists of, or is, DMSO (CAS Number 67-68-5).
- Glycol Ethers
- The second component of the solvent of this invention consists of, or is, a glycol ether, i.e., a compound based on an alkyl ether of ethylene glycol or propylene glycol. These solvents typically have a higher boiling point, together with the favorable solvent properties of lower-molecular weight ethers and alcohols. Representative glycol ethers include, but are not limited to, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. The second component can consist of one or more glycol ethers. In one embodiment the second component consists of one glycol ether. In one embodiment the second component consists of two or more glycol ethers. In one embodiment the second component is an ethylene glycol alkyl ether. In one embodiment the second component is a propylene glycol alkyl ether. In one embodiment the alkyl component of the ethylene or propylene glycol ether is an alkyl group of 2 to 12, or 3 to 10, or 3 to 8, carbon atoms. In one embodiment the second component consists of, or is, ethylene glycol monobutyl ether (CAS Number 111-76-2).
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and N-formyl morpholine as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and N,N-dimethyl propionamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, a glycol ether as the second component, and triethyl phosphate as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and N-formyl morpholine as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and N,N-dimethyl propionamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, DMSO as the first component, a glycol ether as the second component, and triethyl phosphate as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and N-formyl morpholine as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and N,N-dimethyl propionamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a blend consisting of, or consisting essentially of, a sulfoxide as the first component, ethylene glycol monobutyl ether as the second component, and triethyl phosphate as the third component.
- In one embodiment the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and N-formyl morpholine as the third component.
- In one embodiment the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and N,N-dimethyl propionamide as the third component.
- In one embodiment the solvent is a tertiary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a tertiary blend consisting of, or consisting essentially, of DMSO as the first component, ethylene glycol monobutyl ether as the second component, and triethyl phosphate as the third component.
- In one embodiment the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and N,N-dimethyl propionamide as the third component.
- In one embodiment the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine and triethyl phosphate as the third component.
- In one embodiment the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a quaternary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide and triethyl phosphate as the third component.
- In one embodiment the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide and 3-methoxy-N,N-dimethyl propanamide as the third component.
- In one embodiment the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide and triethyl phosphate as the third component.
- In one embodiment the solvent is a quinary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- In one embodiment the solvent is a senary blend consisting of, or consisting essentially of, DMSO as the first component, ethylene glycol monobutyl ether as the second component, and a combination of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- In one embodiment the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 50 to 90 wt % of the first component, from 9 to 40 wt % of the second component, and from 1 to 30 wt % of the third component.
- In one embodiment the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 50 to 90 wt % of DMSO, from 9 to 40 wt % of ethylene glycol monobutyl ether, and from 1 to 30 wt % of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide and triethyl phosphate as the third component.
- In one embodiment the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of the first component, from 1 to 30 wt % of the second component, and from 70 to 90 wt % of the third component.
- In one embodiment the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of DMSO, from 10 to 30 wt % of ethylene glycol monobutyl ether, and from 70 to 90 wt % of at least one of N-formyl morpholine, N,N-dimethyl propionamide, 3-methoxy-N,N-dimethyl propanamide, triethyl phosphate, N,N-dimethyl acetamide; N,N-diethyl acetamide, N,N-diethyl propionamide, N-methyl acetamide, N-methyl propionamide, N-ethyl acetamide, and N-ethyl propionamide as the third component.
- In one embodiment the solvent consists of, or consists essentially of, in weight percent (wt %) based on the weight of the solvent, from 10 to 30 wt % of DMSO, from 10 to 30 wt % of ethylene glycol monobutyl ether, and from 70 to 90 wt % of N,N-dimethyl propionamide, as the third component.
- In one embodiment the solvent has a freezing point of less than (<)−25° C., or <−20° C., or <−15° C., or <−10° C. In one embodiment the solvent has a freezing point from −25° C. or less to −10° C. or more.
- In those embodiments in which the third component consists of more than one substance, e.g., the third component consists essentially of N-formyl morpholine and N,N-dimethyl propionamide and/or 3-methoxy-N,N-dimethyl propanamide and/or triethyl phosphate, etc., the amount of each compound in the third component can vary widely and to convenience. The amount of each individual substance in the third component can vary from 0 to 100 wt %, or from 1 to 99 wt %, or from 10 to 90 wt %, or from 20 to 80 wt % or from 30 to 70 wt %, or from 40 to 60 wt %, or 50 wt %, based on the weight of the component.
- Optional materials that are not essential to the operability of, but can be included in, the solvents of this invention include, but are not limited to, antioxidants, colorants, water scavengers, stabilizers, and the like. These materials do not have any material impact on the efficacy of the solvent for cleaning or stripping electronic parts. These optional materials are used in known amounts, e.g., 0.10 to 5, or 4, or 3, or 2, or 1, weight percent based on the weight of the solvent, and they are used in known ways.
- The solvents of this invention are made using known equipment and known techniques. The individual components of the solvent are commercially available, liquid at ambient conditions (23° C. and atmospheric pressure), and can simply be mixed with one another using conventional mixing equipment and standard blending protocols. The components can be added to one another in any order including simultaneously.
- The solvents of this invention are eco-solvents, i.e., they do not have, or have at a reduced level, the toxicology issues associated with NMP. These solvents are useful for cleaning and/or stripping the surfaces of substrates of contaminants and other unwanted substances, particularly polar contaminants and polar unwanted substances.
- In one embodiment the solvents of this invention are intended as a replacement for NMP and other polar solvents used in the electronics industry. As such, they are used in the same manner as NMP and the other polar solvents in such operations as cleaning and stripping of electronic parts and equipment, and the removal of photoresists from various substrates, e.g., semiconductor substrates, and the removal of polyamic acid polymer residue from polyimide coating equipment, e.g., alignment layer and flexible display substrate coating machine. Typically, these methods or processes include the step of contacting the object or substrate to be cleaned or stripped, or from which a photoresist or a polyamic acid/polyimide residue is to be removed, with the solvent under any of various conditions, e.g., ambient conditions, or at an elevated or reduced temperature, with or without flow or agitation, e.g., printing, spinning, immersing, flushing, vibrating, showering, spraying, etc., for a sufficient period of time to dissolve whatever material, e.g., a contaminant such as poly(amic acid)/polyimide residue, dianhydride, diamine, etc.; a photoresist, and the like, that is to be removed. This contacting step is then typically followed by rinse (one or more, typically with an aqueous liquid such as deionized water) and drying steps. Solvents with a freezing temperature of less than −25° C. can be particularly favored for use in the processes of cleaning and/or stripping electronic parts and equipment.
- The following examples are nonlimiting illustrations of the invention.
- Poly(amic acid), precursor of polyimide: poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid (from Sigma-Aldrich, 15˜16 wt % dissolved in NMP).
- Photoresist: SFP-1400 (from Merck).
- Solvents: N-formyl morpholine (from Accela ChemBio, 98%), dimethyl sulfoxide (DMSO) (from Sinopharm, 99%), triethyl phosphate (from Sinopharm, 99%), 3-methoxy-N,N-dimethyl propanamide (from BOC Science, 98%), N,N-dimethyl propionamide (from Energy Chemical, 98%), and ethylene glycol monobutyl ether (from The Dow Chemical Company, 99%).
- The solvents are designed according to Hansen Solubility Parameter of NMP, DMF, 3-methoxy-N,N-dimethyl propanamide, etc. These commercialized solvents have strong dissolution ability for most electronic materials. The solvents are described in Table 1.
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TABLE 1 Solvents Component A Weight % Component B Weight % Component C Weight % Example 1 dimethyl 64 ethylene glycol 30 N-formyl 6 sulfoxide monobutyl ether morpholine 2 dimethyl 58 ethylene glycol 30 N-formyl 12 sulfoxide monobutyl ether morpholine 3 dimethyl 52 ethylene glycol 30 N-formyl 18 sulfoxide monobutyl ether morpholine 4 dimethyl 65 ethylene glycol 28 N,N-dimethyl 7 sulfoxide monobutyl ether propionamide 5 dimethyl 65 ethylene glycol 20 N,N-dimethyl 15 sulfoxide monobutyl ether propionamide 6 dimethyl 66 ethylene glycol 25 3-methoxy- 7 sulfoxide monobutyl ether N,N-dimethyl propanamide 7 dimethyl 60 ethylene glycol 25 3-methoxy- 15 sulfoxide monobutyl ether N,N-dimethyl propanamide 8 dimethyl 65 ethylene glycol 29 triethyl 6 sulfoxide monobutyl ether phosphate 9 dimethyl 65 ethylene glycol 23 triethyl 12 sulfoxide monobutyl ether phosphate 10 dimethyl 65 ethylene glycol 17 triethyl 18 sulfoxide monobutyl ether phosphate Comparative Example 1 N-methyl-2- 100 pyrrolidone 2 3-methoxy-N,N- 100 dimethyl propanamide 3 monoethanolamine 15 diethylene 20 DI water 65 glycol butyl ether 4 monoethanolamine 30 diethylene 70 glycol butyl ether 5 monoethanolamine 10 N-methyl-2- 70 DI water 20 pyrrolidone - Poly(amic acid) dissolution: A solution of poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid precursor in NMP is contacted with deionized (DI) water or other NMP-insoluble liquid to extract the precursor from the NMP. The poly(amic acid) precursor is then baked at 54° C. for 4 hours to evaporate any residual solvent/liquid before it is dissolved by contact with the test solvent. Results are recorded after 12 hours at 54° C.
- Photoresist stripping: Place 2 milliliters (ml) SFP-1400 photoresist solution onto the surface of glass substrate with a size of 100 millimeters (mm)×100 mm×1 mm. The substrate is spun with a rotation speed of 500 revolutions per minute (rpm) for 10 seconds (s) to spread out the photoresist solution. The rotation speed is then accelerated to 1000 rpm for 30 s to coat the photoresist homogenously and spin out redundant solvent. The coated substrate is heated to evaporate solvent at 130° C. for 10 minutes (min). The stripping step prepares 30 grams (g) example in the container. The baked substrate is placed into the container with shaking, and finally the time is measured for completely removing photoresist from the substrate.
- Poly(amic acid) dissolution: The poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid solubility results of each product are reported in Table 2. The content of polymer in each example and comparative sample is 20% by weight. The performance is judged through the fluidity of the solution. The two examples, N-formyl morpholine/N,N-dimethyl propionamide, and dimethyl sulfoxide/N,N-dimethyl propionamide exhibit good fluidity with low viscosity. N-formyl morpholine/3-methoxy-N,N-dimethyl propanamide shows a certain fluidity and suitable viscosity. However, in comparative samples, 3-methoxy-N,N-dimethyl propanamide, gels occur in the solutions, which represents the oversaturation of polymer. For N-methyl-2-pyrrolidone, although the sample is able to flow, its viscosity is comparatively high. In general, the solubility of poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid in N-methyl-2-pyrrolidone should be 15% by weight for commercial products. For 3-methoxy-N,N-dimethyl propanamide, the related solubility is comparatively lower. Therefore, the solvency for poly(amic acid) of examples is better than comparative samples.
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TABLE 2 Poly(amic acid) (poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid) Solvency Performance of Solvents Example Component A Weight % Component B Weight % Component C Weight % Performance dimethyl 64 ethylene glycol 30 N-formyl 6 ◯ sulfoxide monobutyl ether morpholine dimethyl 58 ethylene glycol 30 N-formyl 12 ◯ sulfoxide monobutyl ether morpholine dimethyl 52 ethylene glycol 30 N-formyl 18 ◯ sulfoxide monobutyl ether morpholine dimethyl 65 ethylene glycol 28 N,N-dimethyl 7 ◯ sulfoxide monobutyl ether propionamide dimethyl 65 ethylene glycol 20 N,N-dimethyl 15 ◯ sulfoxide monobutyl ether propionamide dimethyl 66 ethylene glycol 25 3-methoxy-N,N- 7 ◯ sulfoxide monobutyl ether dimethyl propanamide dimethyl 60 ethylene glycol 25 3-methoxy-N,N- 15 ◯ sulfoxide monobutyl ether dimethyl propanamide dimethyl 65 ethylene glycol 29 triethyl phosphate 6 ◯ sulfoxide monobutyl ether dimethyl 65 ethylene glycol 23 triethyl phosphate 12 ◯ sulfoxide monobutyl ether dimethyl 65 ethylene glycol 17 triethyl phosphate 18 ◯ sulfoxide monobutyl ether Comparative Component Weight % Performance N-methyl-2-pyrrolidone 100 ◯ 3-methoxy-N,N-dimethyl 100 X propanamide Open circle = fluidity; X = high viscosity (no flow) - Photoresist stripping: The photoresist stripping results of each combination are listed in Table 3. The performance is evaluated by stripping time. The example, dimethyl sulfoxide/ethylene glycol monobutyl ether/N,N-dimethyl propionamide can completely strip the coated photoresist from the glass substrate within 15 seconds. The other invented dimethyl sulfoxide/ethylene glycol monobutyl ether based examples require 15 to 20 seconds to strip the photoresist. Water based monoethanolamine/diethylene glycol butyl ether and monoethanolamine/N-methyl-2-pyrrolidone comparative samples Dongji (KR1403516B1) need almost a half-minute for stripping. However the other commercial combination, monoethanolamine/diethylene glycol butyl ether without water content shows relatively slow stripping speed. Therefore, the examples possess better stripping performance on SFP-1400 photoresist.
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TABLE 3 Photoresist (SFP-1400) Stripping Performance of Solvents Component A Weight % Component B Weight % Component C Weight % Performance Example dimethyl 64 ethylene 30 N-formyl 6 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 58 ethylene 30 N-formyl 12 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 52 ethylene 30 N-formyl 18 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 65 ethylene 28 N,N-dimethyl 7 ⊙ sulfoxide glycol propionamide monobutyl ether dimethyl 65 ethylene 20 N,N-dimethyl 15 ⊙ sulfoxide glycol propionamide monobutyl ether dimethyl 66 ethylene 25 3-methoxy- 7 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether dimethyl 60 ethylene 25 3-methoxy- 15 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether dimethyl 65 ethylene 29 triethyl 6 ◯ sulfoxide glycol phosphate monobutyl ether dimethyl 65 ethylene 23 triethyl 12 ◯ sulfoxide glycol phosphate monobutyl ether dimethyl 65 ethylene 17 triethyl 18 ◯ sulfoxide glycol phosphate monobutyl ether Comparative monoethanolamine 15 diethylene 20 DI water 65 Δ glycol butyl ether monoethanolamine 30 diethylene 70 X glycol butyl ether monoethanolamine 10 N-methyl-2- 70 DI water 20 Δ pyrrolidone Circle with a dot = less than (<) 15 seconds; Open circle (i.e., circle without dot) = 15020 seconds; Triangle - 20-30 seconds; and X = greater than or equal to (≥) 30 seconds. - The solvents are designed to have a freezing point lower than −25° C., and faster photoresist stripping and polyamic acid dissolution than NMP. For each blending example, The detailed ratio for each inventive and comparative example is reported in the Table 4.
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TABLE 4 Solvents Component A Weight % Component B Weight % Component C Weight % Example 11 dimethyl 20 ethylene glycol 20 N,N-dimethyl 60 sulfoxide monobutyl propionamide ether 12 dimethyl 10 ethylene glycol 20 N,N-dimethyl 70 sulfoxide monobutyl propionamide ether 13 dimethyl 20 ethylene glycol 30 N,N-dimethyl 50 sulfoxide monobutyl propionamide ether 14 dimethyl 10 ethylene glycol 30 N,N-dimethyl 60 sulfoxide monobutyl propionamide ether 15 dimethyl 30 ethylene glycol 40 N,N-dimethyl 30 sulfoxide monobutyl propionamide ether 16 dimethyl 20 ethylene glycol 40 N,N-dimethyl 40 sulfoxide monobutyl propionamide ether 17 dimethyl 10 ethylene glycol 40 N,N-dimethyl 50 sulfoxide monobutyl propionamide ether Comparative Example 6 N-methyl-2- 100 pyrrolidone 7 3-methoxy-N,N- 100 dimethyl propanamide 8 monoethanolamine 15 diethylene 20 DI water 65 glycol butyl ether 9 monoethanolamine 30 diethylene 70 glycol butyl ether 10 monoethanolamine 10 N-methyl-2- 70 DI water 20 pyrrolidone - Polyamic Acid Dissolution
- The procedure of Examples 1-10 and Comparative Examples 1-5 is repeated here.
- Photoresist Stripping
- The procedure of Examples 1-10 and Comparative Examples 1-5 is repeated here.
- Freeze Testing
- Twenty gram (20 g) samples are prepared and stored in a refrigerator at −25° C. for 24 hours after which the samples are viewed for liquid or solid (frozen) state.
- Polymeric Acid Dissolution
- The poly (pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid solubility results of each product are reported in Table 5. The amount of polymer in each example and comparative sample is 30% by weight. The performance is judged through the viscosity of the solution. All dimethyl sulfoxide/ethylene glycol monobutyl ether based solvents can completely dissolve polyamic acid and exhibit good viscosity, which indicates the invented combinations have equivalent performance with N-methyl-2-pyrrolidone. As for the other comparative sample, 3-methoxy-N,N-dimethyl propanamide, the related solubility is comparatively lower. The solution is hard to flow. Therefore, the solvency for polyamic acid of the inventive examples is good relative to certain commercial products.
-
TABLE 5 Polyamic Acid Solvency Performance of Various Solvents Example Component A Weight % Component B Weight % Component C Weight % Performance dimethyl 20 ethylene 20 N,N-dimethyl 60 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 10 ethylene 20 N,N-dimethyl 70 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 20 ethylene 30 N,N-dimethyl 50 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 10 ethylene 30 N,N-dimethyl 60 ◯ sulfoxide glycol propionamide monobutyl ether Comparative Component Weight % Performance N-methyl-2-pyrrolidone 100 ◯ 3-methoxy-N,N-dimethyl 100 X propanamide ◯ = Low Viscosity X = High Viscosity - Photoresist Stripping
- The photoresist stripping results of each combination are reported in Table 6. The performance is evaluated by stripping time. Dimethyl sulfoxide/ethylene glycol monobutyl ester/N,N-dimethyl propionamide can completely strip the coated photoresist from the glass substrate within 15 seconds. The dimethyl sulfoxide/ethylene glycol monobutyl ester based examples require 15 to 20 seconds to strip the photoresist. Water-based monoethanolamine/diethylene glycol butyl ether and monoethanolamine/N-methyl-2-pyrrolidone comparative samples required close to a half minute for stripping. However the other commercial combination, monoethanolamine/diethylene glycol butyl ether without water content shows relatively slow stripping speed. Therefore, the examples possess better stripping performance on SFP-1400 photoresist.
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TABLE 6 Photoresist Stripping Performance of the Solvents Component A Weight % Component B Weight % Component C Weight % Performance Example dimethyl 20 ethylene 20 N-formyl 60 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 10 ethylene 20 N-formyl 70 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 20 ethylene 30 N-formyl 50 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 10 ethylene 30 N,N-dimethyl 60 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 30 ethylene 40 N,N-dimethyl 30 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 20 ethylene 40 3-methoxy- 40 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether dimethyl 10 ethylene 40 3-methoxy- 50 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether Comparative monoethanolamine 15 diethylene 20 DI water 65 Δ glycol butyl ether monoethanolamine 30 diethylene 70 X glycol butyl ether monoethanolamine 10 N-methyl-2- 70 DI water 20 Δ pyrrolidone ◯ means <20 seconds Δ means 20 to 30 seconds X means >30 seconds - Photoresist Stripping (Frozen)
- Twenty gram (20 g) solvent samples are placed into fifty milliliter (50 mL) glass cylinders. The solvent-containing glass containers and a thermometer are placed into a refrigerator, and the temperature of the refrigerator is set to −25° C. The samples are kept in the refrigerator at −25° C. for 12 hours. The results are reported in Table 7. The physical state of the solvent, i.e., liquid or solid, is determined by visual inspection of the sample in the glass cylinder. All inventive samples are liquid. Among the comparative examples, 3-methoxy-N,N-dimethyl propanamide and monoethanolamine/diethylene glycol butyl ether are liquid. However, N-methyl-2-pyrrolidone, monoethanolamine/diethylene glycol butyl ether/DI water and monoethanolamine/N-methyl-2-pyrrolidone/DI water are solid.
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TABLE 7 Liquid/Solid Status of Solvents are −25° C. Component A Weight % Component B Weight % Component C Weight % Performance Example dimethyl 20 ethylene 20 N-formyl 60 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 10 ethylene 20 N-formyl 70 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 20 ethylene 30 N-formyl 50 ◯ sulfoxide glycol morpholine monobutyl ether dimethyl 10 ethylene 30 N,N-dimethyl 60 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 30 ethylene 40 N,N-dimethyl 30 ◯ sulfoxide glycol propionamide monobutyl ether dimethyl 20 ethylene 40 3-methoxy- 40 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether dimethyl 10 ethylene 40 3-methoxy- 50 ◯ sulfoxide glycol N,N-dimethyl monobutyl propanamide ether Comparative N-methyl-2- 100 X pyrrolidone 3-methoxy-N,N- 100 ◯ dimethyl propanamide monoethanolamine 15 diethylene 20 DI water 65 X glycol butyl ether monoethanolamine 30 diethylene 70 ◯ glycol butyl ether monoethanolamine 10 N-methyl-2- 70 DI water 20 X pyrrolidone ◯ = Liquid X = Frozen (Solid)
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- 2017-01-20 ES ES17735370T patent/ES2901504T3/en active Active
- 2017-01-20 EP EP17735370.3A patent/EP3519896B1/en active Active
- 2017-01-20 WO PCT/CN2017/071798 patent/WO2018058866A1/en active Application Filing
- 2017-01-20 CN CN201780000588.2A patent/CN108139693A/en active Pending
- 2017-01-20 JP JP2017537468A patent/JP6871163B2/en active Active
- 2017-01-20 CA CA3041937A patent/CA3041937A1/en active Pending
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CN115521743A (en) * | 2022-09-11 | 2022-12-27 | 广州天赐高新材料股份有限公司 | Adhesive for semiconductor processing and method for improving semiconductor processing performance |
Also Published As
Publication number | Publication date |
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KR20190059820A (en) | 2019-05-31 |
US10731114B2 (en) | 2020-08-04 |
WO2018058866A1 (en) | 2018-04-05 |
JP6871163B2 (en) | 2021-05-12 |
JP2019532483A (en) | 2019-11-07 |
EP3519896A1 (en) | 2019-08-07 |
ES2901504T3 (en) | 2022-03-22 |
CN108139693A (en) | 2018-06-08 |
EP3519896B1 (en) | 2021-11-17 |
CA3041937A1 (en) | 2018-04-05 |
WO2018058341A1 (en) | 2018-04-05 |
TW201814033A (en) | 2018-04-16 |
EP3519896A4 (en) | 2020-06-03 |
TWI739864B (en) | 2021-09-21 |
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